EP0130058A1 - Catalytic conversion of ethers to esters and alcohols - Google Patents

Catalytic conversion of ethers to esters and alcohols Download PDF

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Publication number
EP0130058A1
EP0130058A1 EP84304217A EP84304217A EP0130058A1 EP 0130058 A1 EP0130058 A1 EP 0130058A1 EP 84304217 A EP84304217 A EP 84304217A EP 84304217 A EP84304217 A EP 84304217A EP 0130058 A1 EP0130058 A1 EP 0130058A1
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Prior art keywords
catalyst
hydrogen
ether
reaction
carbon monoxide
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EP84304217A
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German (de)
French (fr)
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EP0130058B1 (en
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Steven P. Current
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Chevron USA Inc
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Chevron Research and Technology Co
Chevron Research Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to a process for the homologation of ethers to esters and alcohols and is concerned with a process for the conversion of dialkyl ethers to homologous carboxylic acid esters and alcohols by reaction of the ether with hydrogen and carbon monoxide in the presence of a heterogeneous sulphided catalyst.
  • European Patent Application Publication No.31606 describes the preparation of carboxylic acids and esters from carboxylic acid esters having one less carbon atom, carbon monoxide and hydrogen in the presence of a catalyst containing a ruthenium compound, a Group II metal iodide and/or bromide and a further Group VIII metal compound.
  • European Patent Application Publication No.31784 describes the preparation of alkyl carboxylates from lower homologues by reaction with carbon monoxide and hydrogen using a ruthenium, cobalt and iodide catalyst system.
  • European Patent Application Publication No.46128 describes the hydrocarbonylation and/or carbonylation of alkyl carboxylates in the presence of ruthenium, cobalt, vanadium and an iodide promoter.
  • U.S. Patent No.2,623,906 discloses that at pressures above 1,000 atmospheres and in the presence of a cobalt catalyst, primary, secondary and tertiary alcohols react with synthesis gas to form glycol ethers and monohydric alcohols containing at least one more carbon atom per molecule than the original alcohol reactant.
  • U.S. Patent No. 3,285,948 discloses that an improved yield of ethanol from methanol can be obtained by conducting the synthesis gas homologation reaction in the presence of a cobalt catalyst which is promoted with iodine and a metal halide selected from ruthenium halide and osmium halide.
  • U.S. Patent No.4,111,837 discloses a process for producing ethanol which comprises reacting methanol with carbon monoxide and hydrogen in the presence of a catalyst consisting essentially of a methanol-soluble cobalt carbonyl and methanol-insoluble rhenium metal.
  • U.S. Patent No. 4,304,946 discloses a process for producing ethanol from methanol, carbon monoxide and hydrogen which comprises conducting the reaction in the presence of a cobalt sulphide or a mixture of a cobalt sulphide and at least one of a nitrogen-containing compound and a phosphorus compound.
  • a process for the conversion of dialkyl ethers to homologous carboxylic acid esters and alcohols which comprises reacting a dialkyl ether having from two to twenty carbon atoms with hydrogen and carbon monoxide at a temperature in the range from 150 to 350°C and a pressure in the range from 500 psig to 5,000 psig (36 to 353 kg/cm 2 ) in the presence of a heterogeneous sulphided catalyst comprising nickel, optionally in admixture with a co-catalyst selected from the elements of Group VIB of the Periodic Table.
  • the present invention is based on the discovery that dialkyl ethers can be converted to useful oxygenated products having at least one more carbon atom than the starting ether in improved yield and selectivity by utilizing a heterogeneous sulphided catalyst system.
  • An advantage of the process of the present invention lies in the fact that the heterogeneous catalyst employed is easier to separate from the reaction products than the homogeneous catalysts of the prior art.
  • the process of the present invention does not require the use of any soluble catalyst promoters. This is particularly advantageous, since the absence of a halide promoter in the system obviates the need for expensive corrosion resistant equipment.
  • Oxygen-containing carbon compounds which can be obtained with high selectivity by the process of the invention are carboxylic acid esters and alcohols or the secondary products which may be formed therefrom under the reaction conditions in a subsequent reaction, for example, reduction, hydrolysis, condensation or dehydration.
  • the dialkyl ether is charged to a high pressure reactor, and then there is introduced a heterogeneous sulphided catalyst system comprising nickel and, optionally, an element of Group VIB of the Periodic Table.
  • the reactor is pressurized with a mixture containing carbon monoxide and hydrogen and heated for a suitable length of time to give the desired conversion.
  • Liquid and gaseous products and reactants can be easily separated from the catalyst by filtration, distillation or other methods. Unreacted starting materials can be recycled.
  • the products can be isolated by means of one of a number of known methods, including distillation. In some cases it may be advantageous to further process the products. For example, methyl acetate can be easily hydrolyzed to acetic acid.
  • the process of the present invention can also be run in a continuous fashion. This is particularly advantageous as the catalyst is not soluble in the reaction medium.
  • a number of reactor configurations are suitable including fixed or fluid beds, slurry beds or stirred tank reactors. As with a batch reaction, unreacted starting materials can be easily recycled and, if desired, the products can be further processed.
  • dialkyl ethers suitable for use in the present invention will generally contain from two to twenty, preferably two to six, carbon atoms.
  • Suitable dialkyl ethers include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether and methyl propyl ether.
  • a preferred dialkyl ether is dimethyl ether.
  • the reactant dialkyl ether may be diluted with an ether-miscible solvent such as dioxane, tetrahydrofuran, or N-methylpyrolidinone.
  • dimethyl ether is used as the starting ether, the reaction products predominantly formed are methyl acetate and ethanol, with lesser amounts of methyl formate and propanol.
  • the heterogeneous sulphided catalyst system employed in the present process comprises a composite of sulphides of a nickel component and, optionally, a Group VIB component.
  • Group VIB co-catalysts suitable for admixture with the nickel component include chromium, molybdenum and tungsten.
  • a particularly preferred catalyst system comprises nickel and molybdenum.
  • the catalyst system may optionally contain phosphorus or silicon.
  • the support should be a solid, inert material which is relatively insoluble in the solvent employed.
  • Suitable supports include various treated or untreated organic and inorganic supports. Included among these are synthetic and naturally occurring polymers, alumina, silica, titania, silica-alumina, zeolites, glass and carbon. Particularly preferred supports are alumina and silica-alumina.
  • the metals may be added to the support using a method known in the art, such as by impregnation or co-precipitation.
  • the method of loading the catalyst on the support will depend on the nature and composition of the support. Generally, the most convenient method of depositing the metals on the support is by adding a solution of metal salts to the support and subsequently converting them to an insoluble form.
  • An especially suitable catalyst precursor may be prepared by impregnating alumina with an aqueous or organic solution of the metal salts, either together or sequentially, followed by drying and calcining to give the metal oxides.
  • the catalyst may be converted to its active sulphide form by any of a number of conventional procedures.
  • Treatment with hydrogen sulphide or other sulphur-containing compounds such as carbon disulphide, dimethyl disulphide or sulphur, in the presence of hydrogen or synthesis gas is effective. This treatment can be either prior to or concurrent with the ether carbonylation reaction.
  • dialkyl ethers are reacted with carbon monoxide and hydrogen (synthesis gas).
  • Synthesis gas produced by the reaction of carbonaceous material with water is suitable. Mixtures of, for example, carbon dioxide and hydrogen, or carbon monoxide and water, may also be employed. Whether introduced originally, or produced in situ under processing conditions, carbon monoxide and hydrogen are required for the reaction.
  • the relative molar quantities of carbon monoxide and hydrogen present during the reaction can vary in the range from 10:1 to 1:10, and preferably in the range from 3:1 to 1:3.
  • An inert diluent gas such as nitrogen or helium may be included if desired.
  • the carbonylation reaction requires a relatively high pressure for optimum selectivity and yield of product.
  • the pressure should be maintained in the range from 500 to 5,000 psig (36 to 353 kg/cm 2 ), and preferably in the range from 800 to 2000 psig (57 to 142 kg/cm 2 ).
  • the reaction is conducted at a temperature in the range from 150 to 350°C, and preferably in the range from 190 to 290° C .
  • the time that the reactants are in contact with the catalyst will be dependent, among other factors, on the temperature, pressure, ether reactant, catalyst, reactor configuration and the desired level of conversion.
  • the solid catalyst can be easily separated from the generally liquid and gaseous reaction products and unreacted starting materials by, for example, filtration, centrifugation, settling out or distillation.
  • the catalyst can be reused in a subsequent reaction.
  • Unreacted starting materials can be separated from reaction products and are suitable for recycle in the process.
  • the products of the reaction which can be isolated by one of a number of well-known methods, such as distillation, are generally useful as solvents or chemical intermediates. In some cases it may be advantageous to further process the reaction products by well-known means to form other useful products. For example, methyl acetate can be hydrolyzed to acetic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for the conversion of dialkyl ethers to homologous carboxylic acid esters and alcohols comprises reacting a dialkyl ether having from two to twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulphided catalyst comprising nickel, optionally in admixture with a co-catalyst selected from the elements of Group VIB of the Periodic Table, such as molybdenum.

Description

  • This invention relates to a process for the homologation of ethers to esters and alcohols and is concerned with a process for the conversion of dialkyl ethers to homologous carboxylic acid esters and alcohols by reaction of the ether with hydrogen and carbon monoxide in the presence of a heterogeneous sulphided catalyst.
  • An article by M. Hidai et al in Bull. Chem. Soc. Japan, volume 55, pages 3951-52 (1982) describes the homologation of methyl esters, in particular the conversion of methyl acetate to ethyl acetate, with synthesis gas in the presence of a homogeneous ruthenium-cobalt catalyst and a methyl iodide promoter.
  • European Patent Application Publication No.31606 describes the preparation of carboxylic acids and esters from carboxylic acid esters having one less carbon atom, carbon monoxide and hydrogen in the presence of a catalyst containing a ruthenium compound, a Group II metal iodide and/or bromide and a further Group VIII metal compound.
  • European Patent Application Publication No.31784 describes the preparation of alkyl carboxylates from lower homologues by reaction with carbon monoxide and hydrogen using a ruthenium, cobalt and iodide catalyst system.
  • European Patent Application Publication No.46128 describes the hydrocarbonylation and/or carbonylation of alkyl carboxylates in the presence of ruthenium, cobalt, vanadium and an iodide promoter.
  • U.S. Patent No.2,623,906 discloses that at pressures above 1,000 atmospheres and in the presence of a cobalt catalyst, primary, secondary and tertiary alcohols react with synthesis gas to form glycol ethers and monohydric alcohols containing at least one more carbon atom per molecule than the original alcohol reactant.
  • U.S. Patent No. 3,285,948 discloses that an improved yield of ethanol from methanol can be obtained by conducting the synthesis gas homologation reaction in the presence of a cobalt catalyst which is promoted with iodine and a metal halide selected from ruthenium halide and osmium halide.
  • U.S. Patent No.4,111,837 discloses a process for producing ethanol which comprises reacting methanol with carbon monoxide and hydrogen in the presence of a catalyst consisting essentially of a methanol-soluble cobalt carbonyl and methanol-insoluble rhenium metal.
  • U.S. Patent No. 4,304,946 discloses a process for producing ethanol from methanol, carbon monoxide and hydrogen which comprises conducting the reaction in the presence of a cobalt sulphide or a mixture of a cobalt sulphide and at least one of a nitrogen-containing compound and a phosphorus compound.
  • According to the present invention, there is provided a process for the conversion of dialkyl ethers to homologous carboxylic acid esters and alcohols, which comprises reacting a dialkyl ether having from two to twenty carbon atoms with hydrogen and carbon monoxide at a temperature in the range from 150 to 350°C and a pressure in the range from 500 psig to 5,000 psig (36 to 353 kg/cm2) in the presence of a heterogeneous sulphided catalyst comprising nickel, optionally in admixture with a co-catalyst selected from the elements of Group VIB of the Periodic Table.
  • The present invention is based on the discovery that dialkyl ethers can be converted to useful oxygenated products having at least one more carbon atom than the starting ether in improved yield and selectivity by utilizing a heterogeneous sulphided catalyst system.
  • An advantage of the process of the present invention lies in the fact that the heterogeneous catalyst employed is easier to separate from the reaction products than the homogeneous catalysts of the prior art.
  • In addition, it has been found that the process of the present invention does not require the use of any soluble catalyst promoters. This is particularly advantageous, since the absence of a halide promoter in the system obviates the need for expensive corrosion resistant equipment.
  • Oxygen-containing carbon compounds which can be obtained with high selectivity by the process of the invention are carboxylic acid esters and alcohols or the secondary products which may be formed therefrom under the reaction conditions in a subsequent reaction, for example, reduction, hydrolysis, condensation or dehydration.
  • Illustrative of a typical batch procedure, in the process of the invention the dialkyl ether is charged to a high pressure reactor, and then there is introduced a heterogeneous sulphided catalyst system comprising nickel and, optionally, an element of Group VIB of the Periodic Table. The reactor is pressurized with a mixture containing carbon monoxide and hydrogen and heated for a suitable length of time to give the desired conversion. Liquid and gaseous products and reactants can be easily separated from the catalyst by filtration, distillation or other methods. Unreacted starting materials can be recycled. The products can be isolated by means of one of a number of known methods, including distillation. In some cases it may be advantageous to further process the products. For example, methyl acetate can be easily hydrolyzed to acetic acid.
  • The process of the present invention can also be run in a continuous fashion. This is particularly advantageous as the catalyst is not soluble in the reaction medium. A number of reactor configurations are suitable including fixed or fluid beds, slurry beds or stirred tank reactors. As with a batch reaction, unreacted starting materials can be easily recycled and, if desired, the products can be further processed.
  • The dialkyl ethers suitable for use in the present invention will generally contain from two to twenty, preferably two to six, carbon atoms. Suitable dialkyl ethers include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether and methyl propyl ether. A preferred dialkyl ether is dimethyl ether. If desired, the reactant dialkyl ether may be diluted with an ether-miscible solvent such as dioxane, tetrahydrofuran, or N-methylpyrolidinone. When dimethyl ether is used as the starting ether, the reaction products predominantly formed are methyl acetate and ethanol, with lesser amounts of methyl formate and propanol.
  • The heterogeneous sulphided catalyst system employed in the present process comprises a composite of sulphides of a nickel component and, optionally, a Group VIB component. Group VIB co-catalysts suitable for admixture with the nickel component include chromium, molybdenum and tungsten. A particularly preferred catalyst system comprises nickel and molybdenum. In addition, the catalyst system may optionally contain phosphorus or silicon.
  • In carrying out the reaction, it is usually desirable, although not essential, to place the catalyst on a support. Generally, the support should be a solid, inert material which is relatively insoluble in the solvent employed. Suitable supports include various treated or untreated organic and inorganic supports. Included among these are synthetic and naturally occurring polymers, alumina, silica, titania, silica-alumina, zeolites, glass and carbon. Particularly preferred supports are alumina and silica-alumina.
  • The metals may be added to the support using a method known in the art, such as by impregnation or co-precipitation. The method of loading the catalyst on the support will depend on the nature and composition of the support. Generally, the most convenient method of depositing the metals on the support is by adding a solution of metal salts to the support and subsequently converting them to an insoluble form.
  • An especially suitable catalyst precursor may be prepared by impregnating alumina with an aqueous or organic solution of the metal salts, either together or sequentially, followed by drying and calcining to give the metal oxides.
  • The catalyst may be converted to its active sulphide form by any of a number of conventional procedures. Treatment with hydrogen sulphide or other sulphur-containing compounds such as carbon disulphide, dimethyl disulphide or sulphur, in the presence of hydrogen or synthesis gas is effective. This treatment can be either prior to or concurrent with the ether carbonylation reaction.
  • In the process of the present invention dialkyl ethers are reacted with carbon monoxide and hydrogen (synthesis gas). Synthesis gas produced by the reaction of carbonaceous material with water is suitable. Mixtures of, for example, carbon dioxide and hydrogen, or carbon monoxide and water, may also be employed. Whether introduced originally, or produced in situ under processing conditions, carbon monoxide and hydrogen are required for the reaction.
  • The relative molar quantities of carbon monoxide and hydrogen present during the reaction can vary in the range from 10:1 to 1:10, and preferably in the range from 3:1 to 1:3. An inert diluent gas such as nitrogen or helium may be included if desired.
  • The carbonylation reaction requires a relatively high pressure for optimum selectivity and yield of product. The pressure should be maintained in the range from 500 to 5,000 psig (36 to 353 kg/cm2), and preferably in the range from 800 to 2000 psig (57 to 142 kg/cm2).
  • The reaction is conducted at a temperature in the range from 150 to 350°C, and preferably in the range from 190 to 290°C.
  • The time that the reactants are in contact with the catalyst will be dependent, among other factors, on the temperature, pressure, ether reactant, catalyst, reactor configuration and the desired level of conversion.
  • The solid catalyst can be easily separated from the generally liquid and gaseous reaction products and unreacted starting materials by, for example, filtration, centrifugation, settling out or distillation. The catalyst can be reused in a subsequent reaction. Unreacted starting materials can be separated from reaction products and are suitable for recycle in the process.
  • The products of the reaction, which can be isolated by one of a number of well-known methods, such as distillation, are generally useful as solvents or chemical intermediates. In some cases it may be advantageous to further process the reaction products by well-known means to form other useful products. For example, methyl acetate can be hydrolyzed to acetic acid.
  • The following Example is provided to illustrate the invention.
    • EXAMPLE
  • An 18 ml stainless steel reactor was charged with 3.9 g of dimethyl ether and 0.5 g of a catalyst comprising nickel (6%) and molybdenum (15%) oxides, supported on silica-alumina, that had been pretreated with 10% hydrogen sulphide in hydrogen at 325°C. Also included was 0.10 ml of 1,4-dioxane to serve as an internal standard for gas chromatography analysis. The reactor was pressurized to 900 psi (63.3 kg/cm2) with a 2:1 mixture of hydrogen and carbon monoxide and heated with shaking at 2400C for four hours. The reactor was then cooled in an ice bath and vented. The contents were diluted with methanol. Analysis indicated methyl acetate (1.8 mmol) and ethanol (0.5 mmol) as major products. Also formed in lesser amounts were methyl formate and propanol.

Claims (5)

1. A process for converting a dialkyl ether to a homologous carboxylic acid ester and alcohol, which comprises reacting a dialkyl ether having from two to twenty carbon atoms with hydrogen and carbon monoxide at a temperature in the range from 150 to 350°C and a pressure in the range from 500 to 5,000 psig (36 to 353 kg/cm2) in the presence of a heterogeneous sulphided catalyst comprising nickel, optionally in admixture with a co-catalyst selected from the elements of Group VIB of the Periodic Table.
2. A process according to Claim 1, wherein the co-catalyst is molybdenum.
3. A process according to Claim 1 or 2, wherein the sulphided catalyst is present on a support.
4. A process according to Claim 4, wherein the support is alumina or silica-alumina.
5. A process according to any preceding claim, wherein dimethyl ether is converted into methyl acetate and ethanol.
EP84304217A 1983-06-23 1984-06-22 Catalytic conversion of ethers to esters and alcohols Expired EP0130058B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/507,304 US4625050A (en) 1983-06-23 1983-06-23 Ether homologation to esters and alcohols using a heterogeneous sulfided catalyst
US507304 1983-06-23

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EP0130058A1 true EP0130058A1 (en) 1985-01-02
EP0130058B1 EP0130058B1 (en) 1987-03-04

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EP (1) EP0130058B1 (en)
JP (1) JPS6036430A (en)
CA (1) CA1224488A (en)
DE (1) DE3462486D1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU574809B2 (en) * 1984-11-05 1988-07-14 Dow Chemical Company, The Homologation of lower alcohols in a fischer-tropsch process
EP0353722A2 (en) * 1988-08-02 1990-02-07 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Carbonylation process
US6137000A (en) * 1999-02-16 2000-10-24 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using a supported iridium and lanthanide series catalyst
US6160163A (en) * 1999-02-16 2000-12-12 Eastman Chemical Company Method for the vapor-phase carbonylation of lower aliphatic alcohols using a supported platinum catalyst and halide promoter
US6159896A (en) * 1999-02-16 2000-12-12 Eastman Chemical Company Iridium catalyst for carbonylation of lower aliphatic alcohols
US6353132B1 (en) 1999-08-25 2002-03-05 Eastman Chemical Company Vapor phase carbonylation process using group 5 metal promoted iridium catalyst
US6355595B1 (en) 1999-08-25 2002-03-12 Eastman Chemical Company Group 5 metal promoted iridium carbonylation catalyst
US6355837B1 (en) 1999-08-25 2002-03-12 Eastman Chemical Company Vapor phase carbonylation process using group 4 metal promoted iridium catalyst
US6537944B1 (en) 2001-06-20 2003-03-25 Eastman Chemical Company Tungsten promoted catalyst for carbonylation of lower alkyl alcohols
US6548444B2 (en) 2001-06-20 2003-04-15 Eastman Chemical Company Tin promoted iridium catalyst for carbonylation of lower alkyl alcohols
US6617471B2 (en) 2001-06-20 2003-09-09 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using tin promoted iridium catalyst
US6646154B2 (en) 2001-06-20 2003-11-11 Eastman Chemical Company Method for carbonylation of lower alkyl alcohols using tungsten promoted group VIII catalyst

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6177380B1 (en) 2000-05-22 2001-01-23 Eastman Chemical Company Iridium-gold carbonylation co-catalysts
US6506933B1 (en) 2000-05-22 2003-01-14 Eastman Chemical Company Vapor phase carbonylation process using gold catalysts
US6441222B1 (en) 2000-05-22 2002-08-27 Eastman Chemical Company Vapor phase carbonylation process using iridium-gold co-catalysts
US6509293B1 (en) 2000-05-22 2003-01-21 Eastman Chemical Company Gold based heterogeneous carbonylation catalysts
US7087794B2 (en) * 2002-11-15 2006-08-08 Exxonmobil Chemical Patents Inc. Oxygenate conversion in the presence of highly unsaturated compounds
US6717025B1 (en) 2002-11-15 2004-04-06 Exxonmobil Chemical Patents Inc Process for removing oxygenates from an olefinic stream
US7205447B2 (en) * 2002-12-23 2007-04-17 Exxonmobil Chemical Patents Inc. Process for removing aldehydes and/or ketones from an olefinic stream
JP5315515B2 (en) * 2007-03-27 2013-10-16 株式会社Ｉｈｉ Ethanol synthesis method and apparatus
EP1985362A1 (en) * 2007-04-26 2008-10-29 BP Chemicals Limited Process for the carbonylation of dimethyl ether
EP1985608A1 (en) * 2007-04-26 2008-10-29 BP Chemicals Limited Process for the carbonylation of dimethyl ether
WO2008141051A1 (en) * 2007-05-10 2008-11-20 Shell Oil Company Systems and methods for producing oil and/or gas
US20110272151A1 (en) * 2008-07-02 2011-11-10 Andreas Nicholas Matzakos Systems and methods for producing oil and/or gas
WO2018004994A1 (en) 2016-07-01 2018-01-04 Res Usa, Llc Fluidized bed membrane reactor
US9981896B2 (en) 2016-07-01 2018-05-29 Res Usa, Llc Conversion of methane to dimethyl ether
US10189763B2 (en) 2016-07-01 2019-01-29 Res Usa, Llc Reduction of greenhouse gas emission

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2048267A (en) * 1979-05-02 1980-12-10 Mitsubishi Gas Chemical Co Process for producing ethanol
EP0069514A2 (en) * 1981-06-26 1983-01-12 Toyo Engineering Corporation Alcohol carbonylation catalysts

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2593440A (en) * 1948-04-22 1952-04-22 Eastman Kodak Co Manufacture of carboxyl compounds
NL7708158A (en) * 1976-07-28 1978-01-31 Montedison Spa METHOD FOR PREPARING ESTERS.
ZA81783B (en) * 1980-02-19 1982-03-31 Union Carbide Corp Selective homologation of acetals of ethers to monohydric or polyhydric alcohols
FR2488251A1 (en) * 1980-08-07 1982-02-12 Rhone Poulenc Ind PROCESS FOR HYDROCARBONYLATION AND / OR CARBONYLATION OF ALKYL CARBOXYLATES
US4482497A (en) * 1982-09-30 1984-11-13 The Halcon Sd Group, Inc. Preparation of carboxylic acids

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2048267A (en) * 1979-05-02 1980-12-10 Mitsubishi Gas Chemical Co Process for producing ethanol
EP0069514A2 (en) * 1981-06-26 1983-01-12 Toyo Engineering Corporation Alcohol carbonylation catalysts

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU574809B2 (en) * 1984-11-05 1988-07-14 Dow Chemical Company, The Homologation of lower alcohols in a fischer-tropsch process
EP0353722A2 (en) * 1988-08-02 1990-02-07 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Carbonylation process
EP0353722A3 (en) * 1988-08-02 1991-07-31 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Carbonylation process
US5330955A (en) * 1988-08-02 1994-07-19 Union Carbide Chemicals & Plastics Technology Corporation Carbonylation reaction catalysts
US6137000A (en) * 1999-02-16 2000-10-24 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using a supported iridium and lanthanide series catalyst
US6160163A (en) * 1999-02-16 2000-12-12 Eastman Chemical Company Method for the vapor-phase carbonylation of lower aliphatic alcohols using a supported platinum catalyst and halide promoter
US6159896A (en) * 1999-02-16 2000-12-12 Eastman Chemical Company Iridium catalyst for carbonylation of lower aliphatic alcohols
US6353132B1 (en) 1999-08-25 2002-03-05 Eastman Chemical Company Vapor phase carbonylation process using group 5 metal promoted iridium catalyst
US6355595B1 (en) 1999-08-25 2002-03-12 Eastman Chemical Company Group 5 metal promoted iridium carbonylation catalyst
US6355837B1 (en) 1999-08-25 2002-03-12 Eastman Chemical Company Vapor phase carbonylation process using group 4 metal promoted iridium catalyst
US6537944B1 (en) 2001-06-20 2003-03-25 Eastman Chemical Company Tungsten promoted catalyst for carbonylation of lower alkyl alcohols
US6548444B2 (en) 2001-06-20 2003-04-15 Eastman Chemical Company Tin promoted iridium catalyst for carbonylation of lower alkyl alcohols
US6617471B2 (en) 2001-06-20 2003-09-09 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using tin promoted iridium catalyst
US6646154B2 (en) 2001-06-20 2003-11-11 Eastman Chemical Company Method for carbonylation of lower alkyl alcohols using tungsten promoted group VIII catalyst

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Publication number Publication date
JPH0449528B2 (en) 1992-08-11
CA1224488A (en) 1987-07-21
EP0130058B1 (en) 1987-03-04
JPS6036430A (en) 1985-02-25
DE3462486D1 (en) 1987-04-09
US4625050A (en) 1986-11-25

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